Silicon pretreatment for nitride removal

ABSTRACT

Exemplary methods for treating a silicon-containing substrate may include flowing plasma effluents of a hydrogen-containing precursor into a processing region of the semiconductor processing chamber. A silicon-containing substrate may be positioned within the processing region and include a trench formed through stacked layers including alternating layers of silicon nitride and silicon oxide exposing a portion of the silicon-containing substrate. The methods may include contacting the exposed portion of the silicon-containing substrate with the plasma effluents. The methods may include flowing an oxygen-containing precursor into the processing region of the semiconductor processing chamber. The methods may include contacting the exposed portion of the silicon-containing substrate with the oxygen-containing precursor. The methods may also include converting the exposed portion of the silicon-containing substrate to silicon oxide.

TECHNICAL FIELD

The present technology relates to semiconductor processes and equipment. More specifically, the present technology relates to treating exposed materials prior to etching operations.

BACKGROUND

Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a pattern in photoresist into underlying layers, thinning layers, or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process that etches one material faster than another facilitating, for example, a pattern transfer process. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits, and processes, etch processes have been developed with a selectivity towards a variety of materials.

Etch processes may be termed wet or dry based on the materials used in the process. A wet HF etch preferentially removes silicon oxide over other dielectrics and materials. However, wet processes may have difficulty penetrating some constrained trenches and also may sometimes deform the remaining material. Dry etches produced in local plasmas formed within the substrate processing region can penetrate more constrained trenches and exhibit less deformation of delicate remaining structures. However, local plasmas may damage the substrate through the production of electric arcs as they discharge.

Thus, there is a need for improved systems and methods that can be used to produce high quality devices and structures. These and other needs are addressed by the present technology.

SUMMARY

Exemplary methods for treating a silicon-containing substrate may include flowing a hydrogen-containing precursor into a remote plasma region of a semiconductor processing chamber. The methods may include forming a plasma within the remote plasma region to generate plasma effluents of the hydrogen-containing precursor. The methods may include flowing the plasma effluents into a processing region of the semiconductor processing chamber. A silicon-containing substrate may be positioned within the processing region and include a trench formed through stacked layers including alternating layers of silicon nitride and silicon oxide exposing a portion of the silicon-containing substrate. The methods may include contacting the exposed portion of the silicon-containing substrate with the plasma effluents. The methods may include flowing an oxygen-containing precursor into the processing region of the semiconductor processing chamber. The methods may include contacting the exposed portion of the silicon-containing substrate with the oxygen-containing precursor. The methods may also include converting the exposed portion of the silicon-containing substrate to silicon oxide.

In embodiments the method may further include laterally etching the layers of silicon nitride from sidewalls of the trench subsequent the converting. The etching may at least partially remove the converted silicon oxide. The methods may also include repeating the method for at least one additional cycle. The silicon-containing substrate may be etched less than 5 nm during the method. The exposed portion of the silicon-containing substrate converted to silicon oxide may be characterized by a thickness of silicon oxide less than or about 5 nm. The exposed portion of the silicon-containing substrate converted to silicon oxide may be formed beneath a layer of native oxide formed on the silicon-containing substrate. The method may be performed at a chamber operating pressure of less than or about 10 Torr. The method may be performed at a chamber temperature greater than or about 100° C. The oxygen-containing precursor may be water vapor. The water vapor may be flowed into the processing region without plasma enhancement. The hydrogen-containing precursor may be hydrogen.

The present technology also encompasses additional methods of treating a substrate. The methods may include forming a plasma within a remote plasma region of a semiconductor processing chamber containing a hydrogen-containing precursor to generate plasma effluents of the hydrogen-containing precursor. The methods may include flowing the plasma effluents into a processing region of the semiconductor processing chamber. A substrate may be positioned within the processing region, and the substrate may include a trench formed through stacked layers including alternating layers of silicon nitride and silicon oxide exposing a portion of the substrate. The methods may include contacting the exposed portion of the substrate with the plasma effluents. The methods may include flowing water vapor into the processing region of the semiconductor processing chamber. The methods may include contacting the exposed portion of the substrate with the water vapor. The methods may also include forming a layer of oxide on the exposed portion of the substrate.

In some embodiments the methods may also include laterally etching the layers of silicon nitride from sidewalls of the trench subsequent forming the layer of oxide. The etching may at least partially remove the layer of oxide. The methods may also include repeating the method. Repeating flowing the plasma effluents into the processing region of the semiconductor processing chamber may include contacting exposed surfaces of the layers of silicon oxide with the plasma effluents. The plasma effluents may remove fluorine from the layers of silicon oxide. The water vapor may be flowed into the processing region without plasma enhancement. The method may be performed at a chamber temperature greater than or about 200° C.

Such technology may provide numerous benefits over conventional systems and techniques. For example, the processes may protect substrates from undercut. Additionally, the operations of embodiments of the present technology may increase selectivity of subsequently performed etching operations. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosed technology may be realized by reference to the remaining portions of the specification and the drawings.

FIG. 1 shows a top plan view of one embodiment of an exemplary processing system according to embodiments of the present technology.

FIG. 2A shows a schematic cross-sectional view of an exemplary processing chamber according to embodiments of the present technology.

FIG. 2B shows a detailed view of a portion of the processing chamber illustrated in FIG. 2A according to embodiments of the present technology.

FIG. 3 shows a bottom plan view of an exemplary showerhead according to embodiments of the present technology.

FIG. 4 shows exemplary operations in a method according to embodiments of the present technology.

FIGS. 5A-5C show cross-sectional views of substrates being processed according to embodiments of the present technology.

Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aid comprehension and may not include all aspects or information compared to realistic representations, and may include superfluous or exaggerated material for illustrative purposes.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the letter.

DETAILED DESCRIPTION

In transitioning from 2D NAND to 3D NAND, many process operations are modified from vertical to horizontal operations. Additionally, as 3D NAND structures grow in the number of cells being formed, the aspect ratios of memory holes and other structures increase, sometimes dramatically. During 3D NAND processing, stacks of placeholder layers and dielectric materials may form the inter-electrode dielectric or IPD layers. These placeholder layers may have a variety of operations performed to place structures before fully removing the material and replacing it with metal. While the metallization may be incorporated on one side of the cell structure, operations may have previously been performed on the other side of the structure, such as forming floating gates or charge-trap layers. Although these layers may be formed within the memory hole, crosstalk between vertically separated memory cells may occur. One way to reduce this communication may include etching the placeholder material before forming these layers to allow dielectric material to further separate the individual cell material layers from adjacent cells.

Many conventional technologies utilize a wet etch to access each of the cell placeholder materials to perform a lateral etch of placeholders before forming layers, such as the charge-trap layer. However, wet etching may be more robust than other etching techniques, and the wet etching may etch the placeholder materials further than necessary or desired. For example, the wet etching may over etch some features. Additionally, wet etching of small form factor structures may cause pattern collapse or deformation due to surface tension of the etchant. Using wet etchants may also create the need for subsequent operations to remove residues formed within the trenches or holes. Dry etching techniques may also be performed, however many of the dry etchants utilized additionally etch silicon and silicon oxide reducing selectivity of the process. Exposed portions of an underlying silicon substrate may be exposed to the etchants, and due to the relatively weak bonding of silicon, the etchants may etch through the substrate as well.

The present technology overcomes these issues by performing a dry etch process after a protective layer is formed on the exposed portion of the substrate. The protective layer may be formed to limit an effect on the exposed silicon nitride and silicon oxide layer. In this way, the protective material may allow etching operations to be performed that may not remove or may only minimally remove underlying substrate materials.

Although the remaining disclosure will routinely identify specific etching processes utilizing the disclosed technology, it will be readily understood that the systems and methods are equally applicable to deposition and cleaning processes as may occur in the described chambers. Accordingly, the technology should not be considered to be so limited as for use with etching processes or chambers alone. Moreover, although an exemplary chamber is described to provide foundation for the present technology, it is to be understood that the present technology can be applied to virtually any semiconductor processing chamber that may allow the single-chamber operations described.

FIG. 1 shows a top plan view of one embodiment of a processing system 100 of deposition, etching, baking, and curing chambers according to embodiments. In the figure, a pair of front opening unified pods (FOUPs) 102 supply substrates of a variety of sizes that are received by robotic arms 104 and placed into a low pressure holding area 106 before being placed into one of the substrate processing chambers 108 a-f, positioned in tandem sections 109 a-c. A second robotic arm 110 may be used to transport the substrate wafers from the holding area 106 to the substrate processing chambers 108 a-f and back. Each substrate processing chamber 108 a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

The substrate processing chambers 108 a-f may include one or more system components for depositing, annealing, curing and/or etching a dielectric film on the substrate wafer. In one configuration, two pairs of the processing chambers, e.g., 108 c-d and 108 e-f, may be used to deposit dielectric material on the substrate, and the third pair of processing chambers, e.g., 108 a-b, may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers, e.g., 108 a-f, may be configured to etch a dielectric film on the substrate. Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments. It will be appreciated that additional configurations of deposition, etching, annealing, and curing chambers for dielectric films are contemplated by system 100.

FIG. 2A shows a cross-sectional view of an exemplary process chamber system 200 with partitioned plasma generation regions within the processing chamber. During film etching, e.g., titanium nitride, tantalum nitride, tungsten, silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, etc., a process gas may be flowed into the first plasma region 215 through a gas inlet assembly 205. A remote plasma system (RPS) 201 may optionally be included in the system, and may process a first gas which then travels through gas inlet assembly 205. The inlet assembly 205 may include two or more distinct gas supply channels where the second channel (not shown) may bypass the RPS 201, if included.

A cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225, and a substrate support 265, having a substrate 255 disposed thereon, are shown and may each be included according to embodiments. The pedestal 265 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate, which may be operated to heat and/or cool the substrate or wafer during processing operations. The wafer support platter of the pedestal 265, which may comprise aluminum, ceramic, or a combination thereof, may also be resistively heated in order to achieve relatively high temperatures, such as from up to or about 100° C. to above or about 1100° C., using an embedded resistive heater element.

The faceplate 217 may be pyramidal, conical, or of another similar structure with a narrow top portion expanding to a wide bottom portion. The faceplate 217 may additionally be flat as shown and include a plurality of through-channels used to distribute process gases. Plasma generating gases and/or plasma excited species, depending on use of the RPS 201, may pass through a plurality of holes, shown in FIG. 2B, in faceplate 217 for a more uniform delivery into the first plasma region 215.

Exemplary configurations may include having the gas inlet assembly 205 open into a gas supply region 258 partitioned from the first plasma region 215 by faceplate 217 so that the gases/species flow through the holes in the faceplate 217 into the first plasma region 215.

Structural and operational features may be selected to prevent significant backflow of plasma from the first plasma region 215 back into the supply region 258, gas inlet assembly 205, and fluid supply system 210. The faceplate 217, or a conductive top portion of the chamber, and showerhead 225 are shown with an insulating ring 220 located between the features, which allows an AC potential to be applied to the faceplate 217 relative to showerhead 225 and/or ion suppressor 223. The insulating ring 220 may be positioned between the faceplate 217 and the showerhead 225 and/or ion suppressor 223 enabling a capacitively coupled plasma (CCP) to be formed in the first plasma region. A baffle (not shown) may additionally be located in the first plasma region 215, or otherwise coupled with gas inlet assembly 205, to affect the flow of fluid into the region through gas inlet assembly 205.

The ion suppressor 223 may comprise a plate or other geometry that defines a plurality of apertures throughout the structure that are configured to suppress the migration of ionically-charged species out of the first plasma region 215 while allowing uncharged neutral or radical species to pass through the ion suppressor 223 into an activated gas delivery region between the suppressor and the showerhead. In embodiments, the ion suppressor 223 may comprise a perforated plate with a variety of aperture configurations. These uncharged species may include highly reactive species that are transported with less reactive carrier gas through the apertures. As noted above, the migration of ionic species through the holes may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through the ion suppressor 223 may advantageously provide increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn may increase control of the deposition and/or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity, e.g., SiNx:SiOx etch ratios, Si:SiOx etch ratios, etc. In alternative embodiments in which deposition is performed, it can also shift the balance of conformal-to-flowable style depositions for dielectric materials.

The plurality of apertures in the ion suppressor 223 may be configured to control the passage of the activated gas, i.e., the ionic, radical, and/or neutral species, through the ion suppressor 223. For example, the aspect ratio of the holes, or the hole diameter to length, and/or the geometry of the holes may be controlled so that the flow of ionically-charged species in the activated gas passing through the ion suppressor 223 is reduced. The holes in the ion suppressor 223 may include a tapered portion that faces the plasma excitation region 215, and a cylindrical portion that faces the showerhead 225. The cylindrical portion may be shaped and dimensioned to control the flow of ionic species passing to the showerhead 225. An adjustable electrical bias may also be applied to the ion suppressor 223 as an additional means to control the flow of ionic species through the suppressor.

The ion suppressor 223 may function to reduce or eliminate the amount of ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may still pass through the openings in the ion suppressor to react with the substrate. It should be noted that the complete elimination of ionically charged species in the reaction region surrounding the substrate may not be performed in embodiments. In certain instances, ionic species are intended to reach the substrate in order to perform the etch and/or deposition process. In these instances, the ion suppressor may help to control the concentration of ionic species in the reaction region at a level that assists the process.

Showerhead 225 in combination with ion suppressor 223 may allow a plasma present in first plasma region 215 to avoid directly exciting gases in substrate processing region 233, while still allowing excited species to travel from chamber plasma region 215 into substrate processing region 233. In this way, the chamber may be configured to prevent the plasma from contacting a substrate 255 being etched. This may advantageously protect a variety of intricate structures and films patterned on the substrate, which may be damaged, dislocated, or otherwise warped if directly contacted by a generated plasma. Additionally, when plasma is allowed to contact the substrate or approach the substrate level, the rate at which oxide species etch may increase. Accordingly, if an exposed region of material is oxide, this material may be further protected by maintaining the plasma remotely from the substrate.

The processing system may further include a power supply 240 electrically coupled with the processing chamber to provide electric power to the faceplate 217, ion suppressor 223, showerhead 225, and/or pedestal 265 to generate a plasma in the first plasma region 215 or processing region 233. The power supply may be configured to deliver an adjustable amount of power to the chamber depending on the process performed. Such a configuration may allow for a tunable plasma to be used in the processes being performed. Unlike a remote plasma unit, which is often presented with on or off functionality, a tunable plasma may be configured to deliver a specific amount of power to the plasma region 215. This in turn may allow development of particular plasma characteristics such that precursors may be dissociated in specific ways to enhance the etching profiles produced by these precursors.

A plasma may be ignited either in chamber plasma region 215 above showerhead 225 or substrate processing region 233 below showerhead 225. Plasma may be present in chamber plasma region 215 to produce the radical precursors from an inflow of, for example, a fluorine-containing precursor or other precursor. An AC voltage typically in the radio frequency (RF) range may be applied between the conductive top portion of the processing chamber, such as faceplate 217, and showerhead 225 and/or ion suppressor 223 to ignite a plasma in chamber plasma region 215 during deposition. An RF power supply may generate a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

FIG. 2B shows a detailed view 253 of the features affecting the processing gas distribution through faceplate 217. As shown in FIGS. 2A and 2B, faceplate 217, cooling plate 203, and gas inlet assembly 205 intersect to define a gas supply region 258 into which process gases may be delivered from gas inlet 205. The gases may fill the gas supply region 258 and flow to first plasma region 215 through apertures 259 in faceplate 217. The apertures 259 may be configured to direct flow in a substantially unidirectional manner such that process gases may flow into processing region 233, but may be partially or fully prevented from backflow into the gas supply region 258 after traversing the faceplate 217.

The gas distribution assemblies such as showerhead 225 for use in the processing chamber section 200 may be referred to as dual channel showerheads (DCSH) and are additionally detailed in the embodiments described in FIG. 3. The dual channel showerhead may provide for etching processes that allow for separation of etchants outside of the processing region 233 to provide limited interaction with chamber components and each other prior to being delivered into the processing region.

The showerhead 225 may comprise an upper plate 214 and a lower plate 216. The plates may be coupled with one another to define a volume 218 between the plates. The coupling of the plates may be so as to provide first fluid channels 219 through the upper and lower plates, and second fluid channels 221 through the lower plate 216. The formed channels may be configured to provide fluid access from the volume 218 through the lower plate 216 via second fluid channels 221 alone, and the first fluid channels 219 may be fluidly isolated from the volume 218 between the plates and the second fluid channels 221. The volume 218 may be fluidly accessible through a side of the gas distribution assembly 225.

FIG. 3 is a bottom view of a showerhead 325 for use with a processing chamber according to embodiments. Showerhead 325 may correspond with the showerhead 225 shown in FIG. 2A. Through-holes 365, which show a view of first fluid channels 219, may have a plurality of shapes and configurations in order to control and affect the flow of precursors through the showerhead 225. Small holes 375, which show a view of second fluid channels 221, may be distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 365, and may help to provide more even mixing of the precursors as they exit the showerhead than other configurations.

The chambers discussed previously may be used in performing exemplary methods including etching methods and treatment methods. Turning to FIG. 4 is shown exemplary operations in a method 400 according to embodiments of the present technology. Prior to the first operation of the method a substrate may be processed in one or more ways before being placed within a processing region of a chamber in which method 400 may be performed. For example, IPD layers may be formed on the substrate and then one or more memory holes or trenches may be formed through the stacked layers. The IPD layers may include any number of materials, and may include alternating layers of a placeholder material and a dielectric material.

In embodiments the dielectric material may be or include silicon oxide, and the placeholder material may be or include silicon nitride. Although the remaining disclosure will discuss silicon nitride and silicon oxide, any other known materials used in these two layers may be substituted for one or more of the layers. Some or all of these operations may be performed in chambers or system tools as previously described, or may be performed in different chambers on the same system tool, which may include the chamber in which the operations of method 400 are performed.

The method 400 may include flowing a hydrogen-containing precursor into a remote plasma region of a semiconductor processing chamber at operation 405. An exemplary chamber may be chamber 200 previously described, which may include one or both of the RPS unit 201 or first plasma region 215. Either or both of these regions may be the remote plasma region used in operation 405. A plasma may be generated within the remote plasma region at operation 410, which may generate plasma effluents of the hydrogen-containing precursor. The plasma effluents may be flowed to a processing region of the chamber at operation 415. The plasma effluents may interact with the substrate in the processing region at operation 420. As noted, the substrate may include a silicon or silicon-containing substrate or wafer on which a number of layers of material have been formed, such as alternating layers of silicon oxide and silicon nitride. A memory hole or trench may be formed through the stacked layers that extends to the level of the substrate, which may provide an exposed portion of the substrate at the bottom of the hole or trench. In this way, within the hole structure, there may be exposed regions of silicon nitride, silicon oxide, and silicon or some silicon-containing material.

The formation of the hole or trench may have occurred in a different chamber, or at some previous operational step. If performed within the same chamber as method 400, the exposed portion of the surface of the substrate may be relatively clean or neat. However, if the process was performed in a different chamber, or in a different environment, there may be a native oxide formed over the exposed portion of the substrate through the hole or trench. The native oxide may be different from the oxide formed in the alternating layers of the memory structure. For example, while the layers of silicon oxide that may be used to divide memory cells may be a relatively higher quality oxide, native oxide may be a relatively low quality oxide, and may be relatively porous compared to the layers of silicon oxide.

The etching process to remove silicon nitride may have relatively high selectivity to silicon oxide, such as selectivities greater than or about 100:1 or more. However, in some structures, the amount of silicon nitride to be removed may be several nanometers up to a fraction of a micrometer or more. For example, in some embodiments the amount of silicon nitride to be recessed may be tens of nanometers up to hundreds of nanometers. Such an amount of material to be etched may occur over a relatively longer etching time period. The selectivity to oxide of the nitride removal process may operate in part based on an oxide resistance to the etchant, which may include a fluorine-containing material. Fluorine may eventually permeate portions of the silicon oxide materials as well, creating volatile materials that will remove the silicon oxide material as well. However, this process generally includes an incubation period in which the fluorine slowly interacts with the oxide material. The incubation may occur over 2 minutes or more, such as up to 5 minutes, up to 10 minutes, or more depending on the quality of the oxide, the energy of the fluorine, and other processing conditions.

Native oxide, however, may be removed much more quickly due to the porous structure, which may fully expose silicon in the substrate underneath. Because of the process used to remove silicon nitride, the etching process may not be characterized by as high an etch rate relative to silicon, and the exposed silicon may etch in the process. This may cause surface roughness, pitting, as well as etching that may undercut the memory structures, depending on the time the etching process is performed. Accordingly, to protect the underlying silicon, the present technology may form a protective layer of oxide that is of a higher quality than native oxide. However, as the layers of silicon nitride are similarly exposed to the treatment, the treatment may be performed to selectively form oxide on the silicon, while limiting any effect on the exposed regions of silicon oxide and silicon nitride within the trench or hole.

The radical hydrogen effluents may contact the semiconductor structure and permeate the formed trench. The exposed surfaces of silicon oxide and silicon nitride may not be affected, or may be minimally affected by the hydrogen plasma effluents, as the silicon oxide and silicon nitride may have stronger bonding. As the effluents extend through the memory structure, they may contact the exposed portion of the substrate, which may include silicon, and the effluents may have sufficient energy to interact with the relatively weaker bonding of the silicon.

Additionally, in embodiments in which there is an overlying native oxide, the porosity of the native oxide may allow the hydrogen radicals to penetrate the native oxide as well. As the hydrogen radicals penetrate the oxide and interact with the silicon, the hydrogen may hydrogenate the silicon structure, and may also damage the silicon bonding. This may produce dangling bonds that may include dangling Si—H bonds as well as dangling silicon bonds.

The extent of this damage or interaction may be related to the power of the plasma used to form the hydrogen-containing plasma effluents, as well as the distance to be travelled by the formed effluents. For example, by utilizing a remote plasma, a relatively lower plasma power may be used, such as below 5 kW, below or about 1 kW, below or about 500 Watts, or less, which may limit the energy of the plasma effluents. This may also limit the extent to which the plasma effluents interact with the silicon nitride structure, as a local plasma may retain sufficient energy at the wafer level to at least damage upper layers of the silicon nitride contained in the stack. However, this power level when used in remote plasma may be sufficient to interact with the silicon, and may affect the silicon structure to a depth of greater than or about 5 Å, greater than or about 1 nm, greater than or about 1.5 nm, greater than or about 2 nm, greater than or about 2.5 nm, greater than or about 3 nm, greater than or about 3.5 nm, greater than or about 4 nm, greater than or about 4.5 nm, greater than or about 5 nm, or greater, although at this level the energy may be sufficient to affect the silicon nitride. Accordingly, the energy may be sufficient to affect up to 3 nm within the silicon, which may limit interaction with silicon nitride.

Subsequent the plasma effluent interaction with the substrate, method 400 may continue by flowing an oxygen-containing precursor into the processing chamber at operation 425. The oxygen-containing precursor, which may be or include water vapor, may not be passed through a remote plasma prior to being delivered to the substrate processing region, or the plasma may not be engaged through these regions while the oxygen-containing precursor is being delivered. Because the precursor may not have any plasma enhancement, the precursor may not interact with the silicon nitride or silicon oxide layers of the memory stack when the precursor contacts the substrate at operation 430. However, the precursor may penetrate the native oxide, and seek out the dangling bonds. The oxygen-containing precursor may interact with the dangling bonds to provide oxygen forming an oxide layer at operation 435. This process may also be termed a conversion process as the oxide may not be necessarily deposited in some embodiments of the present technology and instead a portion of the silicon substrate may be converted to silicon oxide. Regardless, the present technology encompasses any type of formation of the oxide layer on the substrate, including below a native oxide layer. Once the oxide layer has been formed, a selective etching process may be performed to etch the silicon nitride at optional operation 440.

The hydrogen-containing precursor may be or include hydrogen, a hydrocarbon, or any hydrogen-containing precursor. Example oxygen-containing precursors may be or include water vapor, hydrogen peroxide, oxygen, ozone, or an energized oxygen-containing material, although as previously explained in some embodiments the oxygen-containing precursor may not be plasma enhanced to limit interaction with the silicon nitride materials through the trench that are to be later etched.

Precursors used in the optional silicon nitride etching operation 440 may include a fluorine-containing precursor as well as an oxygen-containing precursor. An exemplary fluorine-containing precursor may be nitrogen trifluoride (NF₃), which may be flowed into the remote plasma region, which may be separate from, but fluidly coupled with, the processing region. Other sources of fluorine may be used in conjunction with or as replacements for the nitrogen trifluoride. In general, a fluorine-containing precursor may be flowed into the remote plasma region and the fluorine-containing precursor may include at least one precursor selected from the group of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluoride, hydrogen fluoride, xenon difluoride, and various other fluorine-containing precursors used or useful in semiconductor processing. The oxygen-containing precursor may include a variety of fluids, and may include one or more of atomic oxygen, molecular oxygen, N₂O, NO, NO₂, ozone, or other oxygen-containing precursors that may be used or useful in semiconductor processes. The precursors may also include any number of carrier gases, which may include nitrogen, helium, argon, or other noble , inert, or useful precursors. The carrier gases may be used to dilute the precursors, which may further reduce etching rates to allow adequate diffusion through the trench.

Process conditions may also impact the operations performed in method 400. Each of the operations of method 400 may be performed during a constant temperature in embodiments, while in some embodiments the temperature may be adjusted during different operations, such as after the pretreatment has been performed. For example, a first temperature may be used during the operations of forming the oxide layer, and then the chamber may be adjusted to a second temperature below the first temperature to perform the optional silicon nitride etch process. For example, the substrate, pedestal, or chamber temperature during the oxide formation may be maintained at a temperature greater than or about 100° C., and in some embodiments the temperature may be maintained greater than or about 150° C., greater than or about 200° C., greater than or about 250° C., greater than or about 300° C., greater than or about 350° C., or greater than or about 400° C. Maintaining the processing, chamber, or substrate temperatures at higher relative temperatures may facilitate the interaction of both the hydrogen plasma effluents as well as the water vapor or oxygen-containing precursor.

In some embodiments, subsequent formation of the oxide layer, the temperature within the processing chamber may be reduced to below or about 100° C. for the optional etch of silicon nitride at operation 440. The temperature may also be maintained below or about 80° C., below or about 60° C., below or about 40° C., below or about 20° C., below or about 0° C., below or about −20° C., below or about −40° C., or lower. Temperature may affect the etching process itself, and higher temperature may produce higher etch rates, increased etching, or other effects. Similarly, lower temperatures may slow the etching operation and allow an oxidation of portions of silicon nitride prior to the etching, or while minimal etching has occurred. Thus, in some embodiments, maintaining a temperature below or about 0° C. may provide more uniform etching amounts of silicon nitride at the top of the trench and at the bottom of the trench. As temperature increases, the etching operations may additionally begin to affect the dielectric regions, and may cause slight rounding of exposed corners or regions of the dielectric material, such as silicon oxide.

The pressure within the chamber may also affect the operations performed, and in embodiments the chamber pressure may be maintained below about 10 Torr, below about 5 Torr, or below about 1 Torr. In embodiments a pressure below or about 1 Torr may allow the precursors or plasma effluents to more easily flow into the trenches or memory holes. However, when the pressure is reduced below about 0.5 Torr, a remote plasma may be affected, and may have reduced stability or may become unstable. As mentioned previously, the remote plasma may include an RPS unit, and may also be a region or portion of the chamber physically partitioned from the processing region of the chamber to limit or eliminate plasma at the wafer level. In some embodiments in which an RPS unit is utilized, a choke may be utilized to maintain a higher pressure within the RPS unit for plasma stability with a lower pressure within a chamber for improved in-trench flow of precursors or plasma effluents. Accordingly, a turbomolecular pump may be utilized in the chamber allowing a chamber pressure down to a few milliTorr, while the RPS is maintained above or about 0.6 Torr.

As noted above, the lateral etch may include oxidizing a portion of the silicon nitride layers adjacent the trench, and may involve forming a fluorinated oxide. The fluorine within or proximate the fluorinated oxide may diffuse through the layer or oxidized portion during the operation to laterally etch the silicon nitride or the oxidized portion of the silicon nitride. Because of the mechanisms of the removal operation, the lateral etch of silicon nitride may impact the oxide layer formed at the bottom of the trench as previously explained, where fluorine utilized in the etch process may erode the formed oxide layer, which may be stronger than native oxide, although may not be as high quality as the layers of silicon oxide, for example. Accordingly, in some embodiments, the lateral etch of silicon nitride may at least partially remove the formed silicon oxide, and may fully remove the formed silicon oxide depending on the amount of nitride removal performed. Accordingly, the present technology may be performed in a number of cycles to refresh the silicon oxide at the bottom of the trench. In some embodiments the process, including the optional lateral etch, may be performed in at least about 2, at least about 3, at least about 4, at least about 5, or more cycles, depending on factors such as the extent of silicon nitride etching to be performed, the rate at which the formed oxide may be removed, or other effects of the process. On completion of the silicon nitride etching, the layer of silicon oxide formed, or layers that get removed through cycling, may limit the degree of etching of the underlying silicon substrate. For example, in embodiments of the present technology, the silicon or silicon-containing substrate may be etched less than or about 5 nm in embodiments, and may be etched less than or about 4 nm, less than or about 3 nm, less than or about 2 nm, less than or about 1 nm, less than or about 5 Å, or less. In some embodiments, aside from the portion of the structure that is converted and/or consumed as silicon oxide in each cycle, the silicon substrate may be substantially or essentially maintained.

A benefit of performing additional cycles may include that the hydrogen plasma effluents may beneficially interact with the silicon oxide layers of the stack to extract fluorine that may be interacting with the layers. As previously discussed, silicon oxide may eventually react to the process for removing silicon nitride after an incubation period in which the fluorine may begin to interact with and extend into the oxide structure. However, although the hydrogen effluents may not react with the silicon oxide itself, or may only minimally interact, the effluent energy may be sufficient to withdraw fluorine that has begun to interact with the silicon oxide, and may remove the fluorine from the layers when the plasma effluents contact the exposed surfaces of the layers of silicon oxide. This may, at least to an extent, refresh the incubation period, and may increase the overall selectivity of the silicon nitride etch process relative to silicon oxide by removing residual etchant from the silicon oxide with each cycle.

Turning to FIGS. 5A-5C are shown cross-sectional views of structure 500 being processed according to embodiments of the present technology. As illustrated in FIG. 5A substrate 505 may have a plurality of stacked layers overlying the substrate, which may be silicon, silicon germanium, or other substrate materials. The layers may include IPD layers including dielectric material 510, which may be silicon oxide, in alternating layers with placeholder material 520, which may be silicon nitride. Placeholder material 520 may be or include material that will be removed to produce individual memory cells in subsequent operations. Although illustrated with only 7 layers of material, exemplary structures may include any of the numbers of layers previously discussed, and it is to be understood that the figures are only schematics to illustrate aspects of the present technology. Trench 530, which may be a memory hole, may be defined through the stacked structure to the level of substrate 505. Trench 530 may be defined by sidewalls 532 that may be composed of the alternating layers of dielectric material 510 and placeholder material 520. As previously discussed, substrate 505 may have a native oxide 507 formed overlying the exposed portion of the substrate within the trench. Depending on the exposure of the substrate to ambient conditions, native oxide 507 may or may not be present.

In FIG. 5B is illustrated a structure after methods according to the present technology have been performed, such as discussed with respect to FIG. 4 above. A remote plasma of a hydrogen-containing precursor may be formed to produce hydrogen or hydrogen-containing plasma effluents 540. The plasma effluents may be delivered to the substrate processing region, where the effluents may interact with the substrate and exposed materials. The effluents 540 may not interact with the layers 510, 520, although the effluents may pass through native oxide 507 and contact substrate 505. The effluents may have sufficient energy to affect the silicon bonding of the substrate, which may create dangling silicon bonds and dangling silicon-hydrogen bonds. Depending on the energy associated with the plasma effluents 540, the effluents may interact within the structure to a distance of up to, about, or greater than about 1 nm, 2 nm, 3 nm, or more as previously described.

FIG. 5C illustrates a structure after further methods or operations according to the present technology have been performed, such as discussed with respect to FIG. 4 above. An oxygen-containing precursor, such as water vapor, may be delivered to the processing chamber, and the precursor may not include any plasma enhancement prior to being delivered. The precursor may flow into the trench and permeate the native oxide 507 if present. The precursor may interact with the dangling bonds to form a silicon oxide layer 545, which may be a converted portion of the silicon substrate 505. Oxide layer 545 may be characterized as a higher quality oxide than native oxide 507, which may provide protection to the substrate 505 from a subsequent silicon nitride etching process to be performed. In embodiments, substrate 505 may show minimal etching at the bottom of the trench during a subsequent nitride etch, and the substrate may be reduced by an amount less than or about 5 nm, and may be reduced to an amount less than or about 3 nm, less than or about 2 nm, less than or about 1 nm, or may be substantially maintained during the lateral etching operations of silicon nitride. This removal may be or include a portion that is converted over one or more cycles of the process. For example, if the oxide layer 545 converts about 1 nm of the silicon substrate 505, and the entire process including laterally etching silicon nitride is performed for three cycles, an amount of about 3 nm of the silicon substrate may be consumed by the process. However, the substrate may not be characterized by pitting or undercut etching by performing pretreatment operations according to the present technology.

In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology. Additionally, methods or processes may be described as sequential or in steps, but it is to be understood that the operations may be performed concurrently, or in different orders than listed.

Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Any narrower range between any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a precursor” includes a plurality of such precursors, and reference to “the layer” includes reference to one or more layers and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, but they do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups. 

The invention claimed is:
 1. A method of treating a silicon-containing substrate, the method comprising: flowing a hydrogen-containing precursor into a remote plasma region of a semiconductor processing chamber; forming a plasma within the remote plasma region to generate plasma effluents of the hydrogen-containing precursor; flowing the plasma effluents into a processing region of the semiconductor processing chamber, wherein a silicon-containing substrate is positioned within the processing region, and wherein the silicon-containing substrate comprises a trench formed through stacked layers including alternating layers of silicon nitride and silicon oxide exposing a portion of the silicon-containing substrate; contacting the exposed portion of the silicon-containing substrate with the plasma effluents; flowing an oxygen-containing precursor into the processing region of the semiconductor processing chamber; contacting the exposed portion of the silicon-containing substrate with the oxygen-containing precursor; and converting the exposed portion of the silicon-containing substrate to silicon oxide.
 2. The method of treating a silicon-containing substrate of claim 1, further comprising laterally etching the layers of silicon nitride from sidewalls of the trench subsequent the converting.
 3. The method of treating a silicon-containing substrate of claim 2, wherein the etching at least partially removes the converted silicon oxide.
 4. The method of treating a silicon-containing substrate of claim 2, further comprising repeating the method for at least one additional cycle.
 5. The method of treating a silicon-containing substrate of claim 4, wherein the silicon-containing substrate is etched less than 5 nm during the method.
 6. The method of treating a silicon-containing substrate of claim 1, wherein the exposed portion of the silicon-containing substrate converted to silicon oxide is characterized by a thickness of silicon oxide less than or about 5 nm.
 7. The method of treating a silicon-containing substrate of claim 1, wherein the exposed portion of the silicon-containing substrate converted to silicon oxide is beneath a layer of native oxide formed on the silicon-containing substrate.
 8. The method of treating a silicon-containing substrate of claim 1, wherein the method is performed at a chamber operating pressure of less than or about 10 Torr.
 9. The method of treating a silicon-containing substrate of claim 1, wherein the method is performed at a chamber temperature greater than or about 100° C.
 10. The method of treating a silicon-containing substrate of claim 1, wherein the oxygen-containing precursor is water vapor.
 11. The method of treating a silicon-containing substrate of claim 10, wherein the water vapor is flowed into the processing region without plasma enhancement.
 12. The method of treating a silicon-containing substrate of claim 1, wherein the hydrogen-containing precursor is hydrogen.
 13. A method of treating a substrate, the method comprising: forming a plasma within a remote plasma region of a semiconductor processing chamber containing a hydrogen-containing precursor to generate plasma effluents of the hydrogen-containing precursor; flowing the plasma effluents into a processing region of the semiconductor processing chamber, wherein a substrate is positioned within the processing region, and wherein the substrate comprises a trench formed through stacked layers including alternating layers of silicon nitride and silicon oxide exposing a portion of the substrate; contacting the exposed portion of the substrate with the plasma effluents; flowing water vapor into the processing region of the semiconductor processing chamber; contacting the exposed portion of the substrate with the water vapor; and forming a layer of oxide on the exposed portion of the substrate.
 14. The method of treating a substrate claim 13, further comprising laterally etching the layers of silicon nitride from sidewalls of the trench subsequent forming the layer of oxide.
 15. The method of treating a substrate of claim 14, wherein the etching at least partially removes the layer of oxide.
 16. The method of treating a substrate of claim 14, further comprising repeating the method.
 17. The method of treating a substrate of claim 16, wherein repeating flowing the plasma effluents into the processing region of the semiconductor processing chamber comprises contacting exposed surfaces of the layers of silicon oxide with the plasma effluents.
 18. The method of treating a substrate of claim 17, wherein the plasma effluents remove fluorine from the layers of silicon oxide.
 19. The method of treating a substrate of claim 13, wherein the water vapor is flowed into the processing region without plasma enhancement.
 20. The method of treating a substrate of claim 13, wherein the method is performed at a chamber temperature greater than or about 200° C. 